Rozprawy doktorskie na temat „Conducting polymers”

The work presented in this thesis is concerned with reduced state conducting polymers, and in particular with poly(pyridine). The electroreductive polymerisation of 2,5-dibromopyridine based on either the Ni(0)(PPh3)4] or [Ni(0)(bpy)3ClO4)2] systems was investigated. The results obtained via both routes are discussed in terms of their respective mechanisms. The initial steps of the polymerisation based on the latter system are analysed using a specially developed kinetic theory. Although the theory was designed specifically to better understand the mechanism of electrosynthesis of poly(pyridine), it has a broader usage for the electrochemist because it describes the limiting current responses of second order ECE reactions at RDEs. The nature of poly(pyridine) prepared by both routes is investigated, and the results obtained are discussed in terms of their structural implications. Although the definitive nature of the polymers is still unclear, a particularly interesting possibility is that the polymers prepared from the [Ni(0)(bpy)3ClO4)2]/2,5-Br2Py/TEAP/AN system are “pyridylonickel strings”. The electrosynthesis of poly(azines) using the [Ni(0)(bpy)3ClO4)2]route is reported, and demonstrates that this strategy can be successfully exploited in the preparation of novel reduced state conducting polymers. Suggestions for further work forming an extension to this thesis are given in the final chapter.

According to different sources, from forty to sixty percent of the overall energy generated in the world today is squandered in waste heat. The existing energy conversion technologies are either close to their efficiency limits or too costly to justify their implementation. Therefore, the development of new technological approaches for waste heat recovery is highly demanded. The field of thermoelectrics can potentially provide an inexpensive, clean and efficient solution to waste heat underutilization, given that a new type of thermoelectric materials capable of meeting those requirements are available. This thesis reports on strategies to optimize a thermoelectric efficiency (ZT) of conducting polymers, more specifically poly(3,4-ethylenedioxythiophene) (Pedot). Conducting polymers constitute a special class of semiconductors characterized by low thermal conductivity as well as electrical conductivity and thermopower that can be readily modified by doping in order to achieve the best combination of thermoelectric parameters. Conducting polymers that have never previously been regarded as hypothetically compatible for thermoelectric energy conversion, can exhibit promising thermoelectric performance at moderate temperatures, which is a sought-after quality for waste heat recovery. A rather substandard thermoelectric efficiency of Pedot-Pss can be markedly improved by various secondary dopants whose addition usually improves polymer’s morphology accompanied by a drastic increase in electrical conductivity and, consequently, in ZT. In order to enable further enhancement in thermoelectric properties, the optimization of the charge carrier concentration is commonly used. The oxidation level of Pedot-Pss can be precisely controlled by electrochemical doping resulting in a tenfold increase of ZT. In contrast to Pedot-Pss, another conducting polymer Pedot-Tos exhibits superior thermoelectric performance even without secondary doping owning to its partially crystalline nature that allows for an improved electronic conduction. With the aid of a strong electron donor, positively doped Pedot-Tos gets partially reduced reaching the optimum oxidation state at which its thermoelectric efficiency is just four times smaller than that of Be2Te3 and the highest among all stable conducting polymers. The downsides associated with chemical doping of Pedot-Tos such as doping inhomogeneity or chemical dopants air sensitivity can be surmounted if the doping level of Pedot-Tos is controlled by acidity/basicity of the polymer. This approach yields similar maximum thermoelectric efficiency but does not necessitate inert conditions for sample preparation. Optimized Pedot-Tos/Pedot-Pss can be functionalized as a p-type material in organic thermogenerators (OTEG) to power low energy electronic devices. If printed on large areas, OTEGs could be used as an alternative technique for capturing heat discarded by industrial processes, households, transportation sector or any natural heat sources for electricity production.

Les polymères conducteurs (PC) sont des matériaux organiques semi-conducteurs très utilisés dans diverses applications technologiques. Les propriétés optiques et conductrices de ces matériaux organiques conjugués résultent de la délocalisation électronique le long des chaînes polymères et dépendent, de ce fait, de la longueur de conjugaison. Les différentes méthodologies de synthèse des PC ont toujours pour finalité la fabrication de nouvelles structures polymères stables dans différents environnements, et dont les propriétés optiques et conductrices seraient ajustables. Néanmoins, les PC qui sont actuellement fabriqués présentent encore un certain nombre de défauts, du fait d’un manque de compréhension et de contrôle du processus de polymérisation.Parmi tous les polymères conducteurs, le poly (3, 4-éthylènedioxythiophène) (PEDOT, un dérivé de polythiophène) et le polypyrrole (PPy) sont déjà utilisés dans plusieurs applications pour leurs propriétés chimiques et physiques. Les PC, comme le PEDOT et le PPy, sont habituellement synthétisés par voie chimique ou électrochimique, la polymérisation étant systématiquement initiée par une étape d’oxydation des monomères. D'autre part, les propriétés complexes des polymères ne peuvent être contrôlées que si une bonne connaissance du procédé de polymérisation est acquise. Dans ce cas, il est possible d’orienter le processus lors de la synthèse (fonctionnalisation, caractère hydrophile, longueur de la chaîne, niveau de dopage) afin d’améliorer les propriétés conductrices des polymères synthétisés.La radiolyse de l'eau représente une méthode simple et efficace qui permet la polymérisation dans des conditions douces (température et pression ambiantes), sans aucun dopant externe, mais qui à notre connaissance n’avait jamais été utilisée seule pour la synthèse de PC. Au sein de notre laboratoire, une méthodologie alternative basée sur l’interaction rayonnement-matière a récemment été utilisée avec succès pour la synthèse de PC nanostructurés en solution aqueuse. Le présent travail est plus spécifiquement consacré à la synthèse de PEDOT et PPy en solution aqueuse et à l'étude de leur mécanisme de croissance par radiolyse pulsée.Grace à l'accélérateur d'électrons ELYSE, l'utilisation de la radiolyse pulsée couplée à la spectroscopie d'absorption résolue dans le temps a permis d'étudier la cinétique des réactions à l’échelle de la nanoseconde et de la milliseconde. Les spectres d’absorption des espèces transitoires impliquées dans le mécanisme réactionnel ont été identifiés grâce à des calculs de chimie quantique. Tout d'abord, la réaction du radical hydroxyle avec les monomères EDOT et Py a été étudiée, ainsi que la polymérisation induite par le rayonnement. Ensuite, l'étude a été transposée à d'autres radicaux oxydants tels que CO3.-, N3. et SO4.- à différents pH. Cette approche a permis de mettre en évidence l'influence des espèces oxydantes sur les premières étapes transitoires lors de l’oxydation des monomères (radical cation, produit d'addition ou radical neutre). Enfin, le faisceau d'électrons a été utilisé comme source de rayonnement ionisant (accumulation de pulses) afin de synthétiser in situ les polymères conducteurs PEDOT et PPy. Ces résultats démontrent que le mécanisme de croissance des PC n'est pas un mécanisme en chaine, mais un mécanisme par stades
Today conductive polymers have many applications in several devices. For these reasons they have received much attention in recent years. Despite intensive research, the mechanism of conducting polymers growth is still poorly understood and the methods of polymerization are limited to two principal ways: chemical and electrochemical synthesis. On the other hand, the complex properties of polymers can be controlled only if a good knowledge of polymerization process is acquired. In this case, it is possible to control the process during the synthesis (functionalization, hydrophilicity, chain length, doping level), and consequently to improve the conductive properties of the synthesized polymers. Water radiolysis represents an easy and efficient method of synthesis comparing to chemical and electrochemical polymerization routes. It enables the polymerization under soft conditions: ambient temperature and pressure, without any external dopant.Among all conductive polymers, poly(3, 4-ethylenedioxythiophene) (PEDOT, a derivate of polythiophene) and polyPyrrole (PPy) have gained some large scale applications for their chemical and physical proprieties. The aim of the present work was the synthesis of PEDOT and PPy in aqueous solution and the study of their growth mechanism by pulsed radiolysis. Thanks to the electron accelerator ELYSE, the use of pulsed radiolysis coupled with time-resolved absorption spectroscopy allowed to study the kinetics of polymerization. The first transient species involved in the mechanism were identified by time resolved spectroscopy and the rate constants were determined.First, the reaction of hydroxyl radicals onto EDOT and Py monomers was studied, as well as the corresponding radiation induced polymerization. Then, the study was transposed to others oxidizing radicals such as CO3.-, N3. and SO4.- at different pHs. This approach allowed to check and to highlight the influence of oxidizing species onto the first transient species produced by monomers oxidation (radical cation, adduct or neutral radical) and onto the resulting morphology and properties of the radiosynthesized polymers. Finally, the electron beam was originally used as a simple electron irradiator in order to in situ synthesize PEDOT and PPy

Thesis (S.M.)--Massachusetts Institute of Technology, Dept. of Mechanical Engineering, 2005.
Includes bibliographical references.
Conducting polymers are a subset of materials within the electroactive polymer class that exhibit active mechanical deformations. These deformations induce stresses and strains that allow for conducting polymers to be used as an actuator for mechanical devices. Incorporation of conducting polymer actuators into mechanical devices requires electrochemical and mechanical characterization of varying polymer sample sizes and their active properties. Of particular interest, is the characterization of macro-length polymer samples, which have yet to be investigated. An understanding of conducting polymer films and their feasibility as an actuator in a mechanical device are required for the development of a conducting polymer based rotary motor. The conducting polymer, polypyrrole, was studied for its feasibility as an actuator for control surfaces on autonomous underwater vehicles. Enhancements to the actuator's performance were addressed following the feasibility study. The development of an electrochemical dynamic mechanical analyzer provides an instrument for characterization of the polymer's properties over a variety of sample sizes and actuation conditions. Finally, the application of polypyrrole as an actuator and possible enhancements combined with the characterization of macro-length polymers provides the necessary tools to develop a rotary motor. Enhancements to polypyrrole actuators in this study account for an increase in tip force of 350% and a seven fold increase in achievable strain.
(cont.) Completion of a novel electrochemical dynamic mechanical analyzer, construction of a finite rotary motor able to subtend angular displacements, and the developed embodiment of a polymer based rotary eccentric motor are accomplished in this study.
by Bryan D. Schmid.
S.M.

Organic coatings are widely used to lower the corrosion rate of metallic structures. However, penetration of water, oxygen and corrosive ions through pores present in the coating results in corrosion initiation and propagation once these species reach the metal substrate. Considering the need for systems that offer active protection with self-healing functionality, composite coatings containing polyaniline (PANI) conducting polymer are proposed in this study. In the first phase of my work, PANI was synthesized by various methods and characterized. The rapid mixing synthesis method was chosen for the rest of this study, providing PANI with high electrical conductivity, molecular structure of emeraldine salt, and morphology of spherical nanoparticles. PANIs doped with phosphoric and methane sulfonic acid revealed hydrophilic nature, and I showed that by incorporating a long-chain alkylphosphonic acid a hydrophobic PANI could be prepared. The second phase of my project was dedicated to making homogenous dispersions of PANI in a UV-curable resin based on polyester acrylate (PEA). Interfacial energy studies revealed the highest affinity of PEA to PANI doped with phosphoric acid (PANI-PA), and no attractive or long-range repulsive forces were measured between the PANI-PA surfaces in PEA.This is ideal for making conductive composites as, along withno aggregation tendency, the PANI-PA particles might come close enough to form an electrically connected network. Highly stable PEA/PANI-PA dispersions were prepared by pretreatment of PANI-PA in acetone followed by mixing in PEA in small portions under pearl-milling. The third phase of my project dealt with kinetics of the free radical polymerization that was utilized to cure the PEA/PANI-PA mixture. UV-vis absorption studies suggested a maximum allowed PANI-PA content of around 4 wt.% in order not to affect the UV curing behavior in the UV-C region. Real-time FTIR spectroscopy studies, using a laboratory UV source, revealed longer initial retardation of the photocuring and lower rates of crosslinking reactions for dispersions containing PANI-PA of higher than 3 wt.%. The presence of PANI-PA also made the formulations more sensitive to changes in UV light intensity and oxygen inhibition during UV curing. Nevertheless, curing of the dispersions with high PANI-PA content, of up to 10 wt.%, was demonstrated to be possible at either low UV light intensities provided the oxygen replenishment into the system was prevented, or by increasing the UV light intensity to very high levels. In the last phase of my project, the PEA and PEA/PANI-PA coatings, cured under high intensity UV lamps, were characterized. SEM analysis showed small PANI-PA particles to be closely packed within the matrix, and the electrical conductivity of the composite films was measured to be in the range of semiconductors. This suggested the presence of a connected network of PANI-PA, as confirmed by investigations of mechanical and electrical variations at the nanoscale by PeakForce TUNA AFM. The data revealed the presence of a PEA-rich layer at the composite-air interface, and a much higher population of the conductive network within the polymer matrix. High current signal was correlated with a high elastic modulus, consistent with the level measured for PANI-PA, and current-voltage studies on the conductive network showed non-Ohmic characteristics. Finally, the long-term protective property of the coatings was characterized by OCP and impedance measurements. Short-term barrier-type corrosion protection provided by the insulating PEA coating was turned into a long-term and active protection by addition of as little as 1 wt.% PANI-PA. A large and stable ennoblement was induced by the coatings containing PANI-PA of up to 3 wt.%. Higher content of PANI-PA led to poorer protection, probably due to the hydrophilicity of PANI-PA facilitating water transport in the coating and the presence of potentially weaker spots in the film. An iron oxide layer was found to fully cover the metal surface beneath the coatings containing PANI-PA after final failure observed by electrochemical testing.

QC 20141103

Esta tesis describe diferentes aplicaciones en el ámbito de la nanobiotecnología de los polímeros conductores generados electroquímicamente. El objetivo principal de la Tesis, que además es el nexo común de los diferentes estudios que se presentan en los Capítulos 4 al 6, es el análisis de las interacciones entre los polímeros conductores sintéticos y diversas entidades biológicas (ADN, proteínas, polisacáridos, pequeños péptidos, drogas, y células). Uno de los retos más importantes de esta Tesis ha sido la caracterización de las interacciones entre los polímeros conductores y el ADN. Los estudios descritos a lo largo del Capítulo 4 ponen en evidencia la existencia de interacciones específicas por puentes de hidrógeno entre plásmidos de ADN y polímeros conductores con sustituyentes polares. Estas interacciones específicas actúan reforzando las interacciones electrostáticas convencionales intrínsecas a la naturaleza cargada de ambos sistemas. Con la intención de obtener la máxima información acerca de estas interacciones, los estudios se han centrado esencialmente en el poli(3,4-etilendioxitiofeno), un polímero conductor con excelentes propiedades y un amplio número de aplicaciones tecnológicas. Los cambios estructurales que se producen en el ADN como consecuencia de la formación de interacciones específicas, las preferencias del polímero conductor por secuencias nucleotídicas bien definidas, así como por con algunas bases nitrogenadas, han permitido proponer un mecanismo que explica la interacción entre las dos sistemas. Este mecanismo, que también se apoya en cálculos teóricos, es totalmente consistente con todos los datos experimentales descritos en esta Tesis. El Capítulo 5 está dedicado al análisis de la interacción entre las moléculas de morfina y los polímeros conductores. Dentro de este contexto general, este el proposito general de este bloque de resultados ha sido optimizar las condiciones necesarias para la detección de esta droga con poli(N-metilpirrol) y con poli(3,4-etilendioxitiofeno). Los estudios se han realizado teniendo en cuenta el efecto de: la morfología del polímero (es decir, se han examinado las tanto películas planas como películas formadas por microestructuras huecas con morfología tipo rosquilla), el tiempo de incubación con la morfina, y el pH del entono. En todos los casos la detección se ha realizado mediante técnicas electroquímicas, que incluyen tanto la espectroscopia de impedancia electroquímica, como la voltametría cíclica. Los resultados reflejan que, en condiciones controladas, los polímeros estudiados muestran no solo una elevada capacidad para capturar las moléculas de morfina, sino también para retenerlas por un período de tiempo largo. Se ha propuesto la fabricación de un dispositivo portátil para la detección de drogas basado en polímeros conductores. El Capítulo 6 es dedicado a la preparación y caracterización de nuevos biocomposites conductores híbridos para aplicaciones en nanobiotecnología y biomedicina. Concretamente, este bloque de resultados presenta la electropolimerización del poli(3,4-etilendioxitiofeno) con diferentes biomoléculas (es decir, un enzima, poli- y oligosacáridos, y un péptido) y la interacción de estos nuevos materiales híbridos con células. Se ha descubierto que, estos biocomposites conservan las propiedades electroquímicas del polímero conductor y que, además, muestran una prominente actividad celular. Los biocomposites que contienen lisozima, forman películas compactas y estables, muestran una elevada actividad bactericida contra las bacterias Gram (+), la cual es debida a que el enzima se libera de forma controlada. La actividad celular observada en los materiales que contienen dextrinas, sugiere que estos biocomposites son candidatos potenciales para la fabricación de soportes celulares. La incorporación de una baja concentración del CREKA en el polímero, tiene un efecto muy positivo en las propiedades electroquímicas del polímero conductor, mejorandolas.
This Thesis reports different nanobiotechnological applications of electrochemically and electrically conducting polymers. The central, and also common, focus of all the studies and experiments described in Chapters 4 to 6 is the interaction between synthetic conducting polymers and bioentities (DNA, proteins, polysaccharides, small peptides, drugs and cells). One of the major challenges of this Thesis consisted on the characterization of the interactions between conducting polymers and DNA. The studies described in Chapter 4 evidenced that specific hydrogen bonding interactions, in addition to conventional electrostatic interactions, are formed between conducting polymers bearing polar groups and plasmid DNA. In order to get more information about such interactions, studies were essentially focused on poly(3,4-ethylenedioxythiophene), a conducting polymer with excellent technological properties. On the basis of both the structural changes undergone by the DNA upon the formation of specific interactions with the conducting polymer and the preferences of the latter towards well-defined nucleotide sequences and bases, a mechanism has been proposed to explain the interaction between the two macromolecules. This mechanism, which is supported by theoretical calculations, is consistent with all the experimental data reported in this Thesis. Chapter 5 is devoted to examine the interaction between morphine molecules and conducting polymers. Within this general context, this block of results is essentially focused on the optimization of the conditions necessary for the detection of this drug using poly(Nmethylpyrrole) and poly(3,4- ehylenedioxythiophene). Studies have been performed considering the effect of: the polymer morphology (i.e. both flat films and films containing hollow microstructures with doughnut-like morphologies have been examined), the time of incubation with morphine, and the pH of the environment. In all cases detection was carried out using electrochemical techniques, which include electrochemical impedance spectroscopy and cyclic voltammetry. Results reflect that, under controlled conditions, the investigated conducting polymers exhibit a high ability to capture morphine molecules, retaining them for a long period of time. In addition, the fabrication of a portable drug detector device based on conducting polymers has been proposed. Finally, Chapter 6 is devoted to the preparation and characterization of new hybrid conducting biocomposites for nanobiotechnological and biomedical purposes. More specifically, this block of the work presents the electropolymerization of poly(3,4-ethylenedioxythiophene) with different biomolecules (i.e. an enzyme, poly- and oligosaccharides, and a small peptide) and the interaction of these new hybrid materials with cells. It was found that, in general, the prepared biocomposites retain the electrical and electrochemical properties of the individual conducting polymer and, in addition, show a prominent cellular activity. Lysozyme-containing biocomposites, which form compact and stable films, exhibit a high bactericidal activity against Gram (+) bacteria, which is promoted by a controlled release of the enzyme. The remarkable cellular activity of dextrins-containing materials suggests that they are potential candidates for the fabrication of cellular scaffolds. Finally, the incorporation of a low concentration of CREKA peptide into the polymer matrix resulted in a very positive effect on the electrochemical properties of the conducting polymer, which were considerably enhanced.

Thick composites (~ 3 mm in thickness) of polypyrrole with electrically insulating porous (polystyrene) and nonporous (polymethyl methacrylate) substrates were prepared using a two-step batch method. In the two-step method, impregnation of volatile (iodine) or nonvolatile (ferric chloride) oxidant in the substrate is followed by in-situ polymerization of pyrrole. Conductivities as high as 10-1 S/cm were obtained in this work in the case of composites of polypyrrole and porous, crosslinked polystyre. Use of the nonvolatile oxidant (ferric chloride) resulted in higher conducting polymer yield, as well as composites having a higher conductivity, thermal stability, and mechanical strength. However, the volatile oxidant (iodine) could be transported to the substrate using supercritical carbon dioxide as the solvent. As a result, partitioning of the oxidant between the solvent phase and the polymer substrate, and hence the distribution of the oxidant in the substrate, could be controlled by manipulation of the pressure. The two-step batch method in which supercritical carbon dioxide is used to facilitate transport and as a solvent for the oxidant was found to be an effective method for the production of thick composites with uniform conductivity, thermal stability, and mechanical strength. Such composites are desired in important practical applications such as rechargeable battery electrodes and electromagnetic interference shielding materials.

Despite the availability of numerous two-dimensional (2D) materials with structural ordering at the atomic or molecular level, direct construction of mesoscale-ordered superstructures within a 2D monolayer remains an enormous challenge. Here, we report the synergic manipulation of two types of assemblies in different dimensions to achieve 2D conducting polymer nanosheets with structural ordering at the mesoscale. The supramolecular assemblies of amphipathic perfluorinated carboxylic acids and block co-polymers serve as 2D interfaces and meso-inducing moieties, respectively, which guide the polymerization of aniline into 2D, freestanding mesoporous conducting polymer nanosheets. Grazingincidence small-angle X-ray scattering combined with various microscopy demonstrates that the resulting mesoscale-ordered nanosheets have hexagonal lattice with d-spacing of about 30 nm, customizable pore sizes of 7–18 nm and thicknesses of 13–45 nm, and high surface area. Such template-directed assembly produces polyaniline nanosheets with enhanced π–π stacking interactions, thereby resulting in anisotropic and record-high electrical conductivity of approximately 41 S cm–1 for the pristine polyaniline nanosheet based film and approximately 188 S cm–1 for the hydrochloric acid-doped counterpart. Our moldable approach creates a new family of mesoscale-ordered structures as well as opens avenues to the programmed assembly of multifunctional materials.

An experimental investigation of the high pressure synthesis of water soluble, self doping conducting polymers is presented. 2- And 3-aminobenzenesulfonic acid and the respective sodium sulfonates have been polymerised. Optimal polymerisation conditions have been determined with respect to yield, conductivity and molecular weight. Reaction parameters such as oxidant, pressure, catalysts, reaction time and temperature and the use of additives were investigated. The minimum pressure required for polymerisation was 7 kbar. An increase in pressure had a negligible effect on polymer characteristics. The polymers were generated in aqueous, non-acidic media, to ensure they were selfdoping when characterised. Conductivities of between 10-6 Scm-1 and 10-3 Scm-1 were measured. The sulfonate salts reacted faster than the sulfonic acids and for both a longer reaction time resulted in higher yields and conductivities. These polymers were completely water soluble, of high molecular weight and able to be cast as thin films. The arylamines 5- and 8-aminonaphthalene-2-sulfonic acid and their respective sodium sulfonates were polymerised at elevated pressure. The naphthalene sulfonate salts polymerised at atmospheric pressure, but displayed a higher molecular weight when reacted under pressure. Generally the naphthalene monomers reacted similarly to the benzene monomers, although there were some differences. Conductivity and yield decreased with increased reaction times and the use of 0.1M equivalents of ferrous sulfate had an negligible effect on the polymers. The polynaphthalenes were highly water soluble, self doping and had conductivities in the order 10-5 to 10-3 Scm-1. A measurement of the activation volume for the polymerisation of 2-methoxyaniline and sodium 8-aminonaphthalene-2-sulfonate was performed. These were determined to be -44 ± 3 cm3mol-1 and -62 ± 10 cm3mol-1 respectively. These large negative values are consistent with rate limiting monomer oxidation.

For some years a dynamic international research effort has focused on developing novel molecular materials which have interesting conducting and semiconducting properties. This thesis is concerned with the investigation of several novel organic polymers which fall into this category. The first part of the work concerns the DC characterisation of three conjugated polymers: poly[2,5-dibutoxy-1-(1'2'-ethynyl)-4-benzene] (A) poly[2,5-dibutoxy-1-(1'4'-buta-1',3'-diynyl)-4-benzene] (B) and poly-p-phenylene-vinylene (C). In their intrinsic state all these materials are quantitatively similar with band gaps of approximately 2.5 eV and room temperature conductivities of around 10^-15 Ω^-1cm^-1. Upon doping with Ferric Chloride the conductivity of Material C is observed to rise dramatically, peaking at around 15 Ω^-1cm^-1. In contrast Materials A and B remain insulating on doping. The temperature dependence of the conductivity and thermopower of doped films of Material C suggests that the mechanism of charge transport changes at a critical temperature (T_c). This increased with increasing doping. Above T_c the transport mechanism is thought to be associated with hopping within a band of localised states which are intrinsic to the material. Below T_c it is likely that transport occurs within localised states associated with the presence of doping ions. The second part of the work concerns the study of the electrochromic materials poly[1,4-dithienylbenzene] (D) and poly[1,3-dithienylbenzene] (E). Both materials have been electrochemically polymerised and form coherent films which undergo reversible colour changes on application of a suitable potential. Display elements based on the materials have reached the 'proof of concept' stage. The displays have contrast ratios of around 6 and exhibit lifetimes greatly in excess of 1000 cycles. The degradation of the displays has in some instances been related to the quality of the film surface and this has been investigated using image analysis techniques.

A new β and N-substituted pyrrole, N-trimethylsilylethoxymethyl-3-methyl-4-pyrrole carboxylate ethyl ester (MPCE-SEM) is synthesised and copolymerised electrochemically with unsubstituted pyrrole to gives free-standing films for conductivity measurements. The electrochemical polymerisation of MPCE-SEM gives only soluble dimers and oligomers rather than polymers because the steric constraints stabilise the oligomeric cation radical of MPCE-SEM. The thiophene monomers containing mesogenic group at the 3-position via an alkyl chain are synthesised and polymerised chemically to give insoluble, infusible polymers and do not exhibit liquid crystalline behaviour. The conductivities of pressed-pellets of the polymer powders are lower than 10^-5S/cm. The electrochemical polymerisation of the thiophene monomers containing mesogenic group of 4-methoxyazbenzen-4'-yloxy or 4-butylazobenzen-4'-yloxy in dichloromethane solution gives a low yield of polymers, which is accompanied by the formation of soluble dimers and oligomers as well as degradation of the resulting polymer and the mesogenic group. Poly{N -11-[(4-cyanobiphenyl-4'-yloxy) undecyl] pyrrole} obtained from chemical polymerisation of the corresponding monomer shows high molecule weight, is soluble in common solvents and fusible showing smectic A liquid crystalline behaviour. This polymer in the melt (175^oC) has a conductivity of 6.6 x 10^-15 S/cm. X-ray photoelectron spectrometry analysis on the melt processed film gives an estimated doping level of an anion every 6-7 monomer units. Electrochemical oxidation of the N-substituted pyrrole monomers gives the electroactive conjugated free-standing polymer films. The conductivities of the free standing polymer films are lower than 10^-4 S/cm. A conducting copolymer containing a side chain liquid crystalline group, poly{N-8-[(4-cyanobiphenyl-4'-yloxy)octyl]-2,5-di(2-thienyl) pyrrole} can be obtained electrochemically from the corresponding monomer. The polymer is slightly soluble in chloroform giving a dark green solution but is not liquid crystalline.

Over the past number of years, polymers with delocalised [pi]-orbitals have been of interest due to their electrical conducting properties. Exposing these polymers to electron donating or accepting dopants, remarkably alters the nature of these materials. In this project it was planned to synthesise and investigate the physical and chemical and electrochemical properties the "polyquinoxaline" family of materials. In order to investigate these materials, synthesis of 5,14-dihydro-5,7,12,14-tetraazapentacene(L5H[sub]2),7,16-dihydro-5,7,9,14,16,18-hexaazaheptacene (L7H[sub]2),7,20-dihydro-5,7,9,11,16,18,20,22-octaazanonacene (L9H[sub]2) and "Polyquinoxaline" (poly[1,6-dihydropyrazino(2,3 -g)-quinoxaline-2,3,8-triyl-7(2H)-ylidene-7,8-dimethylidene was carried out. A number of techniques such as FTIR, solid state NMR, Ultraviolet-Visible spectroscopy have been used in characterising these compounds. Thermogravimetric Analysis and annealing studies of the oligomers were carried out in order to establish optimum crystals growth conditions to aid crystallographic studies. The oligomers (L5H[sub]2) and (L7H[sub]2) were vacuum evaporated on ITO glass substrate. Studies using cyclic voltammetry (CV), and in-situ spectroelectrochemical techniques were used to measure the electrochromic changes and diffusion kinetics in the oligomers upon doping. A comparison with phenazine (L3) has been made where possible in order to complete the available series.

The near future will put a lot of demand on the increasing need for energy production and storage. Issues regarding the modern-day battery technology’s environmental benignity, safety and cost to sustain such demands thus serve as a huge bottleneck, necessitating the research into alternative electrochemical energy storage solutions. Conducting redox polymers are a class of materials which combines the concepts of conducting polymers and redox active molecules to work as fully organic electrode materials. In this work three conducting redox polymers based on 3,4-ethylenedioxythiopene and 3,4-propylenedioxythiopene (EPE) with hydroquinone, catechol and quinizarin pendant groups were investigated. The polymers were electrochemically characterized with regards to their ability to cycle protons (aqueous electrolyte) and cations (non-aqueous electrolyte), their kinetics and charge transport and as cathodes in a battery. In non-aqueous electrolyte, hydroquinone and catechol did not exhibit redox activity in a potential region where the backbone was conducting as they were not redoxmatched. Quinizarin showed redox-matching as concluded by in situ conductance and UV-vis measurements when cycling Na+, Li+, Ca2+ and Mg2+-ions in acetonitrile. Comparison of the kinetics revealed that the rate constant for Ca2+-ion cycling was several magnitudes larger than the rest, and galvanostatic charge/discharge showed that 90% of the polymer capacity was attainable at 5C. An EPE-Quinizarin cathode and metallic calcium anode coin cell assembly displayed output voltages of 2.4 V, and the presented material thus shows promising and exciting properties for future sustainable battery chemistries.

An experimental investigation of the high pressure synthesis of water soluble, self doping conducting polymers is presented. 2- And 3-aminobenzenesulfonic acid and the respective sodium sulfonates have been polymerised. Optimal polymerisation conditions have been determined with respect to yield, conductivity and molecular weight. Reaction parameters such as oxidant, pressure, catalysts, reaction time and temperature and the use of additives were investigated. The minimum pressure required for polymerisation was 7 kbar. An increase in pressure had a negligible effect on polymer characteristics. The polymers were generated in aqueous, non-acidic media, to ensure they were selfdoping when characterised. Conductivities of between 10-6 Scm-1 and 10-3 Scm-1 were measured. The sulfonate salts reacted faster than the sulfonic acids and for both a longer reaction time resulted in higher yields and conductivities. These polymers were completely water soluble, of high molecular weight and able to be cast as thin films. The arylamines 5- and 8-aminonaphthalene-2-sulfonic acid and their respective sodium sulfonates were polymerised at elevated pressure. The naphthalene sulfonate salts polymerised at atmospheric pressure, but displayed a higher molecular weight when reacted under pressure. Generally the naphthalene monomers reacted similarly to the benzene monomers, although there were some differences. Conductivity and yield decreased with increased reaction times and the use of 0.1M equivalents of ferrous sulfate had an negligible effect on the polymers. The polynaphthalenes were highly water soluble, self doping and had conductivities in the order 10-5 to 10-3 Scm-1. A measurement of the activation volume for the polymerisation of 2-methoxyaniline and sodium 8-aminonaphthalene-2-sulfonate was performed. These were determined to be -44 ± 3 cm3mol-1 and -62 ± 10 cm3mol-1 respectively. These large negative values are consistent with rate limiting monomer oxidation.
Thesis (PhD Doctorate)
Doctor of Philosophy (PhD)
School of Science
Full Text

The intention and purpose of the present thesis is to prepare a series of protective coatings using some conducting polymers (CPs) as corrosion inhibitors. The use of organic paints is the most common method for corrosion prevention. Anticorrosive coatings form a class of high-performance systems with a very wide range of applications and being classified in two broad groups: heavy-duty coatings, for high performance, and light-duty coatings, for medium performance. The first class being required for highly aggressive medium, like oil platforms, bridges, chemical industry plants, containers, shipping, and others; the late being employed mainly for outside industrial environments, urban environments, houses, offices, and others. This thesis consists of an overview and a compendium of the following work stages and results: 1. Preparation of nanostructured CPs for corrosion inhibition: Study of the ability of poly(N-methylpyrrole) to form nanostructures and the performance of such nanostructures when act as anticorrosive additive of organic coatings. 2. Partial replacement of metallic zinc dust usually employed in heavy duty protective coatings, by a small concentration of CPs: Study of the use of a small amount of polyaniline emeraldine salt as a partial substitute of metallic zinc dust in marine epoxy primers in order to maintain corrosion inhibition. 3. Evaluation of an environmentally friendly anticorrosive pigment for alkyd priming: Study of the substitution of a high concentration of zinc phosphate, commonly employed in light-duty coatings, by a very low concentration of polyaniline emeraldine base (undoped form), polyaniline emeraldine salt (doped form) and an eco-friendly polythiophene derivative (partially oxidized) in an alkyd coatings and the study of their protective performance using accelerated corrosion assays. 4. Preparation of a novel epoxy coating, based on DMSO as green solvent and free of zinc anticorrosive pigment, and its application on carbon steel protection: Formulation and evaluation of a novel anticorrosive epoxy coating based on DMSO solvent and free of zinc, using polyaniline emeraldine base and poly[2,2’-(3-methylacetate)thiophene] as anticorrosive pigments. All the results derived from the present thesis have been accepted or have been sent for publication in international journals and also reported in some international congresses, as we point below: 1. M. Martí, G. Fabregat, F. Estrany, C. Alemán, E. Armelin, “Nanostructured conducting polymer for dopamine detection”, J.Mater. Chem., 2010, 20, 10652-10660. 2. E. Armelin, M. Martí, F. Liesa, J.I. Iribarren, C. Alemán, “Partial replacement of metallic zinc dust in heavy duty protective coatings by conducting polymer”, Prog. Org. Coat., 2010, 69, 26-30. 3. M. Martí, G. Fabregat, D.S. Azambuja, C. Alemán, E. Armelin, “Evaluation of an environmentally friendly anticorrosive pigment for alkyd primer”, Prog. Org. Coat., 2012, 73, 321–329. 4. M. Martí, L. Molina, C. Alemán, E. Armelin, “Replacement of toxic solvents and anticorrosive pigments used in solvent-borne epoxy coatings by safer functional organic compounds”, submitted for publication in Journal of Hazardous Materials, 2013. 5. M. Martí, E. Armelin, J. Iribarren, C. Alemán. Soluble polythiophenes as anticorrosive additives for marine epoxy paints”, submitted for publication in Materials and Corrosion, 2013. 6. G. Fabregat, M. Martí, F. Estrany, C. Alemán, E. Armelin, “Nanostructured Poly(N-Methylpyrrole) and Its Application in Dopamine Detection”, E-MRS 2010 Spring Meeting. 2010, Strasbourg, France. 7. E. Armelin, M. Martí, F. Estrany, C. Alemán, “Environmentally friendly anticorrosive additive to replace zinc and its compounds in alkyd and epoxy primers”, 12th Mediterranean Congress of Chemical Engineering: shaping the future of chemical engineering. 2011, Barcelona, Spain
El propósito de la presente tesis es preparar una serie de recubrimientos protectores empleando polímeros conductores (CPs) como inhibidores de la corrosión. El uso de pinturas orgánicas es el método más empleado para la prevención de la corrosión. Los recubrimientos anticorrosivos forman una clase de sistemas de alto rendimiento con una amplia variedad de aplicaciones y pueden ser clasificados en dos grandes grupos: recubrimientos de altas prestaciones y recubrimientos de suaves prestaciones. El primero de ellos es el que se emplea en estructuras expuestas a ambientes muy agresivos, tales como: plataformas petrolíferas, puentes, plantas industriales químicas, contenedores, barcos, entre otros; y el último es el que se suele emplear en el exterior de ambientes industriales, ambientes urbanos, casas, oficinas, entre otros. La presente tesis consiste en un compendio de las siguientes etapas del trabajo y resultados: 1. Preparación de CPs nanoestructurados para inhibición de la corrosión: Estudio de la habilidad del Poli(N-metilpirrol) para formar estructuras nanoestructuradas y la actuación de éstas como aditivo anticorrosivo en recubrimientos orgánicos. 2. Sustitución parcial del zinc metálico en polvo habitualmente empleado en pinturas de altas prestaciones, por una pequeña cantidad de CP: Estudio del uso de pequeñas concentraciones de polianilina sal emeraldina (PAni-EB), como sustituto parcial del zinc metálico en polvo, en pinturas de imprimación epoxi marinas, con el objetivo de mantener la inhibición a la corrosión. 3. Evaluación de pigmentos anticorrosivos amigables con el medio ambiente para pinturas de imprimación alquídicas: Estudio de la sustitución de una elevada concentración de fosfato de zinc, generalmente empleado en recubrimientos de suaves prestaciones, por una concentración muy baja de PAni-EB (forma no-dopada), PAni-ES (forma dopada) y un derivado del politiofeno (parcialmente dopado) en un recubrimiento alquídico, y el estudio de sus capacidades protectoras empleando ensayos de corrosión acelerados. 4. Preparación de una nueva pintura epoxi, basada en DMSO como disolvente ecológico y libre de pigmento anticorrosivo de zinc, y su aplicación para la protección de acero al carbono: Formulación y evaluación de una nueva pintura epoxi basada en DMSO como solvente y empleando PAni-EB y poli[2, 2’-(3-metilacetato)tiofeno] como nuevos pigmentos anticorrosivos. Todos los resultados obtenidos en la presente tesis han sido aceptados o han sido enviados para publicación en revistas internacionales; además, algunos resultados han sido divulgados recientemente en congresos internacionales, tal y como se describe abajo: 1. M. Martí, G. Fabregat, F. Estrany, C. Alemán, E. Armelin, “Nanostructured conducting polymer for dopamine detection”, J. Mater. Chem., 2010, 20, 10652-10660. 2. E. Armelin, M. Martí, F. Liesa, J.I. Iribarren, C. Alemán, “Partial replacement of metallic zinc dust in heavy duty protective coatings by conducting polymer”, Prog. Org. Coat., 2010, 69, 26-30. 3. M. Martí, G. Fabregat, D.S. Azambuja, C. Alemán, E. Armelin, “Evaluation of an environmentally friendly anticorrosive pigment for alkyd primer”, Prog. Org. Coat., 2012, 73, 321–329. 4. M. Martí, L. Molina, C. Alemán, E. Armelin, “Replacement of toxic solvents and anticorrosive pigments used in solvent-borne epoxy coatings by safer functional organic compounds”, enviado para publicación en Journal of Hazardous Materials, 2013. 5. M. Martí, E. Armelin, J. Iribarren, C. Alemán. Soluble polythiophenes as anticorrosive additives for marine epoxy paints”, enviado para publicación en Materials and Corrosion, 2013. 6. G. Fabregat, M. Martí, F. Estrany, C. Alemán, E. Armelin, E-MRS 2010 Spring Meeting. 2010, Strasbourg, France. 7. E. Armelin, M. Martí, F. Estrany, C. Alemán, 12th Mediterranean Congress of Chemical Engineering: shaping the future of chemical engineering. 2011, Barcelona, Spain.

Carbon nanotubes and conducting polymers are both interesting for their unique electrochemical properties that make them well suited to use in electrochemical capacitors (sources of high power pulses of electrical energy) and actuators (artificial muscles). In the case of carbon nanotube films, it is their high surface area and electrical conductivity that makes them attractive, particularly in terms of their fast response times. In contrast, the redox chemistry of conducting polymers enables them to achieve large charge storage capacities and dimensional changes in response to potential cycling (often several orders of magnitude larger than those of carbon nanotubes). This thesis reports on the structure and electrochemical properties of composites of multi-walled nanotubes and conducting polymers (polypyrrole and poly(3-methylthiophene)) in addition to their performance in electrochemical capacitors and actuators. The composite film growth conditions were manipulated so as to merge the desirable properties of multi-walled nanotubes with those of conducting polymers. The results composite films were capable of charge storage capacitances, response times and cycle lives superior to those of pre conducting polymer films produced and tested using similar conditions. The alignment, concentration, production route, dimensions and chemical treatment of the carbon nanotubes were all found to play an important role in determining the nanostructure, doping and electrochemical behaviour of the composite films produced. The electrochemical capacitors tested illustrated the power and energy gains that are possible when using carbon nanotube-conducting polymer composite films. Composite film actuators made from multi-walled nanotubes and polypyrrole demonstrated the importance of orienting the nanotubes perpendicular to the desired direction of actuation in order to improve actuation kinetics (through increased electrical conductivity) without constraining actuation of the conducting polymer.

The work described in this thesis concentrates on chemically modified heterocyclic conducting polymers based upon pyrrole, thiophene and indole monomers with -particular emphasis placed upon carboxylic acid substituents. A brief description of the electrochemistry of chemically modified poly(pyrroles) is given with an explanation of the problems associated with the chemical modifications. A reasonable understanding of the properties of chemically modified poly(thiophenes) has been achieved. In particular the properties of poly(3-thiopheneacetic acid) have been characterised in both aqueous and nonaqueous solution using standard electrochemical techniques in conjunction with reflectance FFIR studies. Finally the understanding of poly(indole) and poly(5-carboxyindole) electrochemistry has been greatly improved especially with regards to the chemical structure of each polymer, which was elucidated from several reflectance FTIR studies. The characterisation of the electrochemical growth and the aqueous electrochemistry of poly(5-carboxyindole) are the areas in which the greatest advances have been made. The techniques of reflectance FTIR spectroscopy, UV/vis spectroscopy and impedance spectroscopy have aided the study of poly(5-carboxyindole) immensely. More studies need to be performed before a fuller understanding of these polymeric systems is achieved and the final chapter gives suggestions for further work which will add to the information given in this thesis.

The preparation and characterisation of a number of fluorinated monomers capable of electrochemical polymerisation is described. Their electrochemical characteristics and the products of polymerisation are discussed 4,5,6,7-Tetrafluoroisothianaphthene was synthesised and its chemistry investigated. Attempts to electrochemically polymerise this to give a potentially narrow band-gap conducting polymer were generally unsuccessful. Other analogous monomers were also found to be difficult to polymerise by this method. New fluorinated polyphenylylenevinylene oligomers and polymers have been prepared. In addition, potential routes to high molecular weight polytetrafluorophenylenevinylenes have been being investigated. Oligomeric poly-2,3,5,6-tetrafluorophenylenevinylenes were prepared via a self nucleophilic displacement of the para fluorine in cis and trans organometallic derivatives of corresponding cis and trans 1-halo- 2-pentafluorphenylethenes.The attempted preparation of poly 2,3,5,6-tetrafluorophenylene- vinylene via two different soluble precursor derivatives is described. 2,3,5,6-tetrafluoro-l,4-xylene-bis(dialkyl sulphonium halides) were prepared with view to the preparation of soluble precursor derivatives of F-PPV. Preliminary work polymerising 2,3,5,6-tetrafluorobenzene- 1,4-diethanal with 1,4-dilithium-2,3,5,6-tetrafluorobenzene did provide polyalcohol type precursor polymers to F-PPV, but requires further developement.

Conducting polymers based on heterocyclic organic systems have found a wide and varied number of applications from fast pH sensors to stealth coatings and drug delivery systems. What is surprising, however, is that very little is known about the actual mechanism by which electrical conduction through these systems occurs. Ac impedance spectroscopy was used along with cyclic voltammetry and rotating disc electrode techniques, to electrochemically characterise polymers formed from indole-5-carboxylic acid (15CA). Physical parameters were obtained from the ac spectra by mathematically modelling the results to a novel transmission line developed during the course of the thesis. Investigations of poly(15CA) have shown that the polymer film undergoes substantial morphological changes on extensive cyclic over the course of a number of weeks. This change has been followed by the used of impedance spectroscopy. It has been found that, on electropolymerisation, the polymer is deposited in compact trimer stacks with extensive π delocalisation occurring between the trimer units. This allows the polymer metallic like conduction with fast electron transfer between the polymer/electrolyte interface and the electrode/polymer interface. These observations have been verified using rotating disc techniques along with Koutecky-Levich analysis. It has been found that there is very little solvent/electrolyte in the film initially. Ac spectra at relatively high potentials (300-500mV) have shown the presence of a kinetic barrier consistent with the injection of positive ions into the polymer pores.

Poly(3-alkylthiophene)s are amongst the most technologically promising organic conducting polymers owing to their high stability in both the doped and undoped states. The possibility of complex formation between these polymers and transition metal ions (Fe3+, Cu2+, Ag", Ni2+ and Au3+) was investigated in the solid state and in aprotic solvents. In this thesis the background literature relating to these polymers is reviewed, and the aims of the work described. The practical work is then reported, initially the preparation and characterisation of pure poly(3-alkylthiophene)s, and an attempt to prepare regioregular poly(3-hexylthiophene). 3-Alkylthiophenes were polymerised in the presence of transition metal cations and the pure polymers were reacted (chemically and electrochemically) with the metal cations. A full analysis of the polymers' properties reaction is recorded. The polymers' metal ion contents were determined by elemental analysis as well as by thermogravimetric analysis. Electronic absorption and Fourier- Transform infrared spectroscopy were used to detect whether or not complexation had occurred, and if so whether it acted through the sulphur or through the 7t-backbone of the polymer. The incorporation of transition metals into the polymer structure was found to generate greater interchain electron transfer, so enhancing the electrical conductivity of the polymers. The electrical conductivity of the prepared polymers were therefore measured (using the Van der Pauw four-probe technique) before and after reaction with metal ions. The incorporation of copper into poly(3-alkylthiophene)s gave the best indications that complexation had occurred. Almost all of the transition metals that were used gave an increase in the conductivity. Infrared spectroscopy ofpoly-rnethylthiopheue) showed an enhancement of the asymmetric deformation vibration whereas in poly(3-hexylthiophene) a new low-frequency band was observed which can be assigned to the Cu-S bond vibration. Thermal analysis showed that incorporating transition metals into the polymer structure gave the polymers increased thermal stability. Model complexes were prepared in order to simulate the type of complexation which occurred when transition metal cations interact with the polymer structure. The attempted complexation of bithiophene with copper(TI) perchlorate gave the best-characterised product. A preliminary study was undertaken of the feasibility of producing self-ordered aromatic/heterocyclic monomers, by intercalation into inorganic host materials. Polymerisation was attempted by mild oxidative coupling, with the aim of producing relatively defect-free, high molecular weight polymers. Materials were characterised both before and after intercalation, and also after polymerisation, by powder X-ray diffraction, thermogravimetry and Fourier-Transform infrared spectroscopy. The expansion of the inter-Iaytr spacing, together with molecular modelling calculations, indicated the orientation of the molecules within the host, and hence gave some data to predict whether polymerisation would be likely to occur easily. The intercalation of organic/heterocyclic compounds into a MPS3 host proved to be quite successful. When lattice expansion had been observed, there was evidence that the presence of aromatic molecules had caused strong deformation of the thiophosphate units.